Azolylamidine compounds and herbicidal compositions

ABSTRACT

New azolylamidines of the formula ##SPC1## 
     Wherein 
     n is an integer from 0 to 5, 
     R 1  is halogen, alkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, halophenoxy or haloalkyl; 
     R 2  and R 3 , independently of one another, are each hydrogen, alkyl, alkoxyalkyl, cycloalkyl, alkoxy or alkoxycarbonylalkyl, of, preferably not more than 7 carbon atoms; or taken together, represent a lower alkylene bridge which can be interrupted by one or more hetero-atoms; and 
     Az represents an azolyl radical selected from imidazol-1-yl, pyrrol-1-yl, pyrazol-1-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl or 1,2,3-triazol-1-yl, 
     And their salts are outstandingly effective herbicides showing particularly selective action.

This invention relates to certain new azolylamidine compounds, toherbicidal compositions containing them, and to their use as herbicides.

It is known, from German Auslegeschrift (German Published SpecificationNo.) 1,089,210 and U.S. Pat. No. 3,399,233 that guanidines, especially2-phenyl-1,1,3,3-tetramethyl-guanidine, can be used for combating weeds.However, the activity of these compounds is not always entirelysatisfactory if low amounts and low concentrations are used.

The present invention provides, as new compounds, azolyl-amidines of theformula ##SPC2##

In which

n is 0, 1, 2, 3, 4 or 5,

R¹ is halogen, alkyl, alkoxy, alkylthio, halogenoalkoxy,halogenoalkylthio, halogenophenoxy or halogenoalkyl, the R¹ substituentsbeing selected independently of one another when n is greater than 1,preferably R¹ contains no more than 6 carbon atoms;

R² and R³ , independently of one another, are each hydrogen, alkyl,alkoxyalkyl, cycloalkyl, alkoxy or alkoxycarbonylalkyl, of, preferablynot more than 7 carbon atoms; or, taken together, represent a loweralkylene bridge which can be interrupted by one or more hetero-atoms orhetero-groups and which, together with the adjoining nitrogen, forms athree-membered, five-membered or six-membered, heterocyclic ring and

Az represents an azolyl radical selected from imidazol-1-yl,pyrrol-1-yl, pyrazol-1-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol- 4-yl or1,2,3-triazol-1-yl, the said azolyl radicals optionally carrying one ormore substituents selected from lower alkyl (of up to 6 carbon atoms)aryl, halogen and nitro and/or optionally containing one or more fusedbenzene rings,

And their salts with physiologically tolerated acids.

The compounds of this invention have been found to display excellentherbicidal properties.

Surprisingly, the new azolyl-amidines according to the invention andtheir salts with physiologically tolerated acids show a substantiallygreater herbicidal potency than the guanidines known from the state ofthe art, for example 2-phenyl-1,1,3,3-tetramethyl guanidine, which ischemically the nearest active compound. The compounds according to theinvention thus represent an enrichment of the art.

Preferably R¹ is chlorine, alkyl of from 1 to 4 carbon atoms (forexample methyl), alkoxy of from 1 to 3 carbon atoms (for examplemethoxy), alkylthio of from 1 to 3 carbon atoms (for examplemethylthio), halogenophenyloxy (especially chlorophenoxy) orhalogenoalkoxy, halogenoalkylthio or halogenoalkyl of from, in eachcase, 1 or 2 carbon atoms and 2 to 5 halogen atoms (especially chlorineand fluorine, as in trifluoromethoxy, pentafluoroethoxy,trifluoromethylthio and difluorochloromethythio); R² and R³ are eachhydrogen, alkyl or alkoxy of from in either case 1 to 4 (especially 1 to3) carbon atoms, alkoxyalkyl or alkoxycarbonylalkyl of from, in eithercase, 1 to 3 carbon atoms in the alkoxy moiety and 1 to 2 carbon atomsin the alkyl moiety, or cycloalkyl of from 3 to 7 carbon atoms,(especially of from 5 to 7 carbon atoms), or R² and R³ conjointly forman alkylene bridge which can be interrupted by one or two hetero-atoms,selected from oxygen and sulfur, or by the hetero-grouping --NH-- or--NCH₃ --, and which forms, with the adjoining nitrogen atom, athree-membered, five-membered or six-membered heterocyclic ring; and Azis one of the radicals ##SPC3##

the substituent "Alk" here denoting alkyl (preferably of from 1 to 4carbon atoms).

The present invention also provides a process for the preparation of anazolyl-amidine of formula (I) or a salt thereof, in which aphenyliminocarbamic acid halide of the general formula ##SPC4##

or a hydrogen halide adduct thereof, of the formula ##SPC5##

in which

R¹, r², r³ and n have the above-mentioned meanings and

Hal is halogen, especially chlorine,

is reacted with an azole of the formula

    Az--H                                                      (III),

in which

Az has the above-mentioned meaning,

in the presence of an acid-binding agent and optionally in the presenceof a polar solvent. The azolyl-amidines (I) obtainable according to theinvention can be converted into the salts by reaction with acidsaccording to customary methods; conversely the salts of theazolyl-amidines, also obtainable according to the invention, can beconverted into the free azolyl-amidines (I) by treatment with bases,according to customary methods.

If 4-chlorophenylimino-chlorocarbonic acid dimethylamide or itshydrochloride and 1,2,4-triazole are used as starting materials, thecourse of the reaction can be represented by the following equation:##SPC6##

In accordance with the tautomeric character of 1,2,4-triazole ##SPC7##

the reaction of 1,2,4-triazole with phenyliminocarbamic acid halides offormula (II) or their hydrogen halide adducts of formula (IIa) can alsoresult in derivatives of 1,3,4-triazole, depending on the reactionconditions and/or the method of working up. Thus, in the reaction of2,5-dichlorophenyliminochlorocarbonic acid dimethylamide or itshydrochloride with 1,2,4-triazole, given by way of an example, it is attimes possible that in addition to theN-(2,5-dichlorophenyl)-N',N'-dimethyl-1,2,4-triazolyl-(1)-amidine, theisomeric N-(2,5-dichlorophenyl)-N',N'-dimethyl-1,2,4-triazolyl-(4)-amidine of the formula ##SPC8##

is also formed; the latter can, however, be isolated (see Example 5hereinafter).

The carbamic acid halides of formula (II) and their hydrogen halideadducts of formula (IIa), which can be used according to the invention,are in part known (see French Pat. No. 1,256,873). The carbamic acidhalides of formula (II) which have not previously been described in theliterature can be prepared by reacting known isocyanide-dichlorides ofthe general formula ##SPC9##

in which

R¹ and n have the above-mentioned meanings

with an equimolar amount of an amine of the general formula ##STR1## inwhich R² and R³ have the above-mentioned meaning

in accordance with methods known in principle (see GermanAuslegeschriften (German Published Specifications Nos.) 1,170,931 and1,089,210). The hydrogen halide adducts of formula (IIa) which have notpreviously been described in the literature can be prepared by reacting1-phenylureas of the general formula ##SPC10##

in which

R¹, r², r³ and n have the above-mentioned meanings,

with chlorinating agents, such as phosphorus pentachloride, in a mannerknown in principle. See German Auslegeschrift (German PublishedSpecification No.) 1,129,161.

The following may be mentioned as examples of the starting compounds ofthe formula (II) and (IIa); phenylimino-chlorocarbonic acidethyleneamide, phenylimino-chlorocarbonic acid amide,phenylimino-chlorocarbonic acid dimethylamide,phenylimino-chlorocarbonic acid diethylamide,4-chlorophenylimino-chlorocarbonic acid dimethylamide,4-chlorophenylimino-chlorocarbonic acid methylmethoxyamide, 4-chlorophenylimino-chlorocarbonic acid diethylamide,4-chlorophenyliminochlorocarbonic acid methylpropylamide,4-chlorophenyliminochlorocarbonic acid methylisopropylamide,4-chlorophenyliminochlorocarbonic acid methylbutylamide,3-trifluoromethylphenylimino-chlorocarbonic acid dimethylamide,4-methylphenyliminochlorocarbonic acid dimethylamide,3-methylphenylimino-chlorocarbonic acid dimethylamide,4-ethylphenylimino-chlorocarbonic acid dimethylamide,4-butylphenylimino-chlorocarbonic acid dimethylamide,4-ethoxyphenylimino-chlorocarbonic acid dimethyl-amide,4-methoxyphenylimino-chlorocarbonic acid dimethylamide,4-methylthiophenylimino-chlorocarbonic acid dimethylamide,4-trifluoromethylphenylimino-chlorocarbonic acid dimethylamide,4-chlorophenylimino-chlorocarbonic acid ethyleneamide,3,4-dichlorophenylimino-chlorocarbonic acid ethyleneamide,3,4-dichlorophenylimino-chlorocarbonic acid dimethylamide,3,4-dichlorophenylimino-chlorocarbonic acid methylmethoxyamide,2,4-dichlorophenylimino-chlorocarbonic acid dimethylamide,2,5-dichlorophenylimino-chlorocarbonic acid dimethylamide,2,6-dichlorophenylimino-chlorocarbonic acid dimethylamide,2,3-dichlorophenylimino-chlorocarbonic acid dimethylamide,3-chloro-4-methoxyphenylimino-chlorocarbonic acid dimethylamide,3-chloro-4-methylthiophenyliminochlorocarbonic acid dimethylamide,3-chloro-4-ethylthiophenyliminochlorocarbonic acid dimethylamide,3-chloro-4-ethylthiophenylimino-chlorocarbonic acid methylbutylamide,2,3,4-trichlorophenylimino-chlorocarbonic acid dimethylamide,3,4,5-trichlorophenylimino-chlorocarbonic acid dimethylamide,2,4,5-trichlorophenylimino-chlorocarbonic acid dimethylamide,2,4,6-trichlorophenylimino-chlorocarbonic acid dimethylamide,2,3,6-trichlorophenylimino-chlorocarbonic acid dimethylamide,1,2,3,4,5-pentachlorophenylimino-chlorocarbonic acid dimethylamide,4-chloro-2-trifluoromethylphenylimino-chlorocarbonic acid dimethylamide,3-chloro-4-trifluoromethylphenylimino-chlorocarbonic acid dimethylamide,4-chloro-3-trifluoromethylphenylimino-chlorocarbonic acid dimethylamide,4-chloro-2-methylphenylimino-chlorocarbonic acid dimethylamide,4-chloro-3-methylphenylimino-chlorocarbonic acid dimethylamide,3-chloro-4-methoxyphenylimino-chlorocarbonic acid dimethylamide,3-chloro-4-methylphenylimino-chlorocarbonic acid dimethylamide,3-chloro-4-methylphenyliminochlorocarbonic acid methylbutylamide,phenylimino-chlorocarbonic acid (ethoxycarbonylmethyl)methylamide,phenyliminochlorocarbonic acid methylcyclohexylamide,phenyliminochlorocarbonic acid ethylamide,4-trifluoromethylphenyliminochlorocarbonic acid dimethylamidehydrochloride, 2-methyl-4-trifloromethylphenylimino-chlorocarbonic aciddimethylamide hydrochloride, 3-trifluoromethylphenylimino-chlorocarbonicacid dimethylamide hydrochloride,4-trifluoromethoxyphenylimino-chlorocarbonic acid dimethylamidehydrochloride, 3-pentafluoroethoxyphenylimino-chlorocarbonic aciddimethylamide hydrochloride,3-chloro-4-trifluoromethoxyphenyliminochlorocarbonic acid dimethylamidehydrochloride, 3-chloro-4-methylthiophenylimino-chlorocarbonic acidmethylbutylamide, 3-trifluoromethoxyphenylimino-chlorocarbonic aciddimethylamide hydrochloride,3-chloro-4-chlorodifluoromethylthiophenylimino-chlorocarbonic aciddimethylamide hydrochloride, 3,4-dichlorophenylimino-carbonic acidmethylmethoxyamide hydrochloride, 4-chlorophenylimino-chlorocarbonicacid dimethylamide hydrochloride, 3,4-dichlorophenylimino-chlorocarbonicacid methylbutylamide hydrochloride,3,4-dichlorophenylimino-chlorocarbonic acid morpholide hydrochloride,3,4-dichlorophenylimino-chlorocarbonic acid piperide hydrochloride,3,4-dichlorophenylimino-chlorocarbonic acid piperazide hydrochloride,phenylimino-chlorocarbonic acid cyclohexylamide hydrochloride,3,4-dichlorophenylimino-chlorocarbonic acid 4'-methylpiperazidehydrochloride, phenyliminochlorocarbonic acid pyrolidinylamidehydrochloride and (4-chlorophenoxy)phenylimino-chlorocarbonic aciddimethylamide hydrochloride.

The following starting materials of formula (III) may be mentioned:pyrrole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, imidazole,2-methylimidazole, 2-ethylimidazole, 2-propylimidazole,2-isopropylimidazole, benzotriazole, benzimidazole, indole,4-methylimidazole, 4-ethylimidazole, 4-nitroimidazole,2-methyl-4-nitroimidazole, 2-methyl-5-nitroimidazole,4-methyl-5-nitroimidazole, 2,4-dimethyl-imidazole,2-methyl-4-ethylimidazole, 2-chloroimidazole, 4,5-dichloroimidazole and2,4,5-trichloroimidazole.

The azoles of formula (III) used as starting materials are known.

The azolyl-amidines (I) according to the invention can be converted intosalts by reaction with acids, preferably with physiologically toleratedacids, according to customary methods. Examples of such physiologicallytolerated acids are the hydrogen halide acids, for example hydrobromicacid and, in particular, hydrochloric acid, and also phosphoric acid,nitric acid, monofunctional and bifunctional carboxylic acids andhydroxycarboxylic acids, such as, for example, acetic acid, maleic acid,succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,sorbic acid and lactic acid, as well as 1,5-naphthalenedisulfonic acid.

Polar organic solvents can be used as diluents for the reactionaccording to the invention. Preferred solvents include chlorinatedhydrocarbons, such as chlorobenzene; ketones, such as acetone or diethylketone; nitriles, such as acetonitrile; and ethers, such astetrahydrofuran and dioxane.

All acid acceptors usually employed can be used as acid binding agents.Preferably, alkali metal hydroxide, alkali metal carbonates and organicbases are used: piperidine, pyridine, triethylamine and sodium carbonateare particularly suitable. Furthermore, an excess of an azole of theformula (III) can also be employed as the acid-burning agent.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the reaction is carried out at between 0° and 80° C, preferablybetween 20° and 50° C. The reaction is generally carried out undernormal pressure.

In carrying out the process according to the invention, 1 to 1.1 molesof azole of formula (III) and 1 to 1.1 moles of acid-binding agent aregenerally employed per 1 mole of starting material of formula (II). Permole of starting material of formula (IIa), 1 to 1.5 moles of azole offormula (III) are generally employed, together with either 1 to 1.2moles of acid-binding agent, if it is desired to obtain a salt (hydrogenhalide adduct) of an azolyl-amidine as the end product, or with 2 to 2.5moles of acid-binding agent, if it is desired to obtain a freeazolyl-amidine (I) as the end product.

To isolate the free azolyl-amidines (I), the hydrohalide of theacid-binding agent, which may have been produced, is first filtered off,and the filtrate is freed of the solvent in vacuo. The oil which remainsis taken up in an organic solvent and the solution is washed with wateruntil free of salt. The organic phase is dried, the solvent is distilledoff and the resulting oil is purified by distillation and, if itcrystallizes out, by recrystallization.

To isolate salts of the azolyl-amidines, the hydrohalide of theacid-binding agent, which may have separated out, is again firstfiltered off. The filtrate is freed of the solvent in vacuo, leaving theazolyl-amidine salt; should this be obtained in an oily form, it can becaused to crystallize by trituration with a suitable solvent, such asethyl acetate.

The preparation of the compounds of the present invention is illustratedin the following preparative Examples:

EXAMPLE 1 Preparation of N-phenyl-N' ,N'-dimethyl-imidazolyl(1)-amidine##SPC11##

Variant a

1.095 kg (5 moles) of phenyliminochlorocarbonic acid dimethylamidehydrochloride were suspended in 2 l of acetonitrile. 374 g (5.5 moles)of imidazole were introduced into this suspension with external cooling,during which addition the temperature rose to about 50°°C. 1.111 kg (11moles) of triethylamine were then added dropwise with external coolingand under a reflux condenser.

After stirring for 15 hours at room temperature, the triethylammoniumchloride which had separated out was filtered off. The solvent of thefiltrate was then distilled off under reduced pressure, the residue wastaken up in 2 l of methylene chloride and the solution was washed withwater until free of salt. The organic phase was dried over sodiumsulfate and freed of the solvent in vacuo and the oily residue wastriturated with diisopropyl ether; this caused it to become crystalline.

835 g (78% of theory) of N-phenyl-N' ,N'-dimethylimidazolyl-(1)-amidineof melting point 70° C were obtained.

Variant b

22 g (0.1 mole) of phenyliminochlorocarbonic acid dimethylamidehydrochloride were introduced into a solution of 6.8 g (0.1 mole) ofimidazole in 300 ml of acetonitrile, whilst cooling. 10.1 g (0.1 mole)of triethylamine were added dropwise. After stirring for 15 hours, thetriethylammonium chloride which had separated out was filtered off andthe filtrate was freed of the solvent.

The oil which remained was dissolved in 500 ml of water and a solutionof 4 g (0.1 mole) of sodium hydroxide in 100 ml of water was added. Theaqueous solution was extracted with ether and the ether solution wasdried over anhydrous sodium sulfate, filtered and freed of the solvent.

20.5 g (96% of theory) of N-phenyl-N' ,N'-dimethylimidazolyl-(1)-amidineof melting point 70° C were obtained.

The starting material could be prepared as follows: ##SPC12##

326 g (2 moles) of N-phenyl-N',N'-dimethyl-urea were mixed with 417 g (2moles) of phosphorus pentachloride in a stirring apparatus equipped witha descending condenser, and the mixture was heated to 60°-80° C, untilthe reaction started. Thereafter, the temperature of the reactionmixture rose, with vigorous evolution of hydrogen chloride, and aboutone-third of the phosphorus oxychloride formed distilled off.

After the reaction had subsided, the mixture was heated to 100° C for 4hours whilst stirring and was then cooled to 60° C, and 300 ml of ethylacetate were added. After stirring for 15 hours, the crystals which hadseparated out were filtered off at room temperature.

367 g (83.5% of theory) of phenyliminochlorocarbonic acid dimethylamidehydrochloride of melting point 140° C were obtained. A further 28 g wereobtained from the filtrate by distilling off the solvent in vacuo andtriturating the residue with ethyl acetate.

Total yield: 395 g (90% of theory).

EXAMPLE 2 Preparation ofN-4-chlorophenyl-N',N'-dimethylpyrazolyl-(1)-amidine ##SPC13##

38.1 g (0.15 mole) of 4-phenyliminochlorocarbonic acid dimethylamidehydrochloride were introduced into a solution of 10.2 g (0.15 mole) ofpyrazole in 500 ml of acetonitrile and 15.2 g (0.15 mole) oftriethylamine were then added dropwise. After stirring for 15 hours atroom temperature, the triethylammonium chloride which had separated outwas filtered off and the filtrate was freed of the solvent in vacuo.

42 g (98% of theory) ofN-4-chlorophenyl-N',N'-dimethyl-pyrazolyl-(1)-amidine hydrochloride ofmelting point 170° C was obtained. ##SPC14##

The hydrochloride was dissolved in 500 ml of water, the aqueous solutionwas filtered and an aqueous solution containing 6 g (0.15 mole) ofsodium hydroxide was added. The aqueous solution was extracted withether and the ether phase was worked up in the usual manner.

34 g (91.5% of theory) ofN-4-chlorophenyl-N',N'-dimethyl-pyrazolyl-(1)-amidine of melting point76° C were obtained.

EXAMPLE 3 Preparation ofN-2,4,6-trichlorophenyl-N',N'-dimethyl-1,2,4-triazolyl-(1)-amidine##SPC15##

A solution of 3.5 g (0.05 mole) of 1,2,4-triazole and 5.1 g (0.05 mole)of triethylamine in 150 ml of acetonitrile was added dropwise to asolution of 14.3 g (0.05 mole) of2,4,6-trichlorophenyliminochlorocarbonic acid dimethylamide in 150 ml ofacetonitrile at room temperature. After stirring for 15 hours at roomtemperature, the triethylamine chloride which had separated out wasfiltered off and the filtrate is freed of the solvent in vacuo. Theresidue was dissolved in chloroform and the solution was washed withwater until free of salt. The organic phase was dried and filtered andthe solvent was distilled off. The resulting oil was caused tocrystallize by trituration with diethyl ether. 8.5 g (53% of theory) ofN-2,4,6-trichlorophenyl-N',N'-dimethyl-1,2,4-triazolyl-(1)-amidine ofmelting point 140° C were obtained.

The starting material could be prepared as follows: ##SPC16##

89 g (0.37 mole) of 2,4,6-trichlorophenylisocyanide dichloride weredissolved in 1,000 ml of acetone. Dimethylamine was passed into thissolution at 0° C, whilst cooling. After the exothermic reaction hadended, the dimethylammonium chloride which had separated out wasfiltered off and the solvent of the filtrate was distilled off. Aftertriturating the semicrystalline mass with a little diisopropyl ether andsubsequently filtering, 55.6 g (61% of theory) of2,4,6-trichlorophenyliminochlorocarbonic acid dimethylamide of meltingpoint 82° C were obtained.

EXAMPLE 4 Preparation ofN-(3,4-dichlorophenylimino)-N',N'-dimethyl-pyrazolyl-(1)-amidinehydrochloride ##SPC17##

10.2 g (0.14 mole) of pyrazole were dissolved in 300 ml of acetonitrileand 43.5 g (0.15 mole) of 3,4-dichlorophenyliminochlorocarbonic aciddimethylamide hydrochloride were added in portions. After the exothermicreaction had subsided, 15.2 g (0.15 mole) of triethylamine were addeddropwise, whilst stirring. After stirring for 15 hours at roomtemperature, the triethylammonium chloride which had separated out wasfiltered off, the filtrate was freed of the solvent in vacuo and the oilwhich remained was triturated with acetone. The residualtriethylammonium chloride which had separated out was filtered off. Thesolvent of the filtrate was again distilled off and the resulting oilwas triturated with ethyl acetate.

40 g (83% of theory) ofN-(3,4-dichlorophenylimino)-N',N'-dimethyl-pyrazolyl-(1)-amidinehydrochloride of melting point 120° C were obtained.

EXAMPLE 5 Preparation ofN-2,5-dichlorophenylimino-N,N'-dimethyl-1,2,4-triazolyl-(4)-amidine##SPC18##

28.8 g (0.1 mole) of 2,5-dichlorophenyliminocarbonic acid dimethylamidehydrochloride were suspended in 300 ml of acetonitrile and 27.6 g (0.4mole) of 1,2,4-triazole and 40.4 g (0.4 mole) of triethylamine wereadded. After standing for 15 hours at room temperature, thetriethylammonium chloride which had separated out was filtered off, thefiltrate was freed of the solvent in vacuo, the residue was dissolved inethyl acetate and the solution was washed with water until free of salt.After drying, and distilling off the ethyl acetate, the crystallinemixture was triturated with ether.

12.5 g (44% of theory) ofN-2,5-dichlorophenylimino-N,N'-dimethyl-1,2,4-triazolyl-(4)-amidine ofmelting point 165° C were obtained. The nuclear resonance spectrumshowed, for the azole protons, a singlet with the intensity of 2-protonsat 8.78 ppm (δ CH₂ at 60 MH_(z), TMS as the internal standard, d-DMSO asthe solvent). The ether solution, after distilling off the ether andtriturating the residual oil with diisopropyl ether, gave 6 g (22% oftheory) ofN-2,5-dichlorophenylinino-N',N'-dimethyl-1,2,4-triazolyl-(1)-amidine ofmelting point 120° C. The nuclear resonance spectrum showed, for theazole protons, two signals each with the intensity of one proton, at 8.2and 8.78 ppm (δ CH₂ at 60 MH_(z), TMS as the internal standard, d-DMSOas the solvent).

The compounds listed in Table 1 which follows can be preparedanalogously:

                                      Table 1                                     __________________________________________________________________________     ##STR2##                                                                     Example                                     Physical                          No.   R.sup.1   n R.sup.2                                                                              R.sup.3                                                                              Az          characteristics                   __________________________________________________________________________    6    3,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR3##   m.p  60° C                 7      --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR4##   n.sub.D.sup.20 1.5910             8    3-CF.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR5##   n.sub.D.sup.20 1.5340             9    3-Cl, 4-OCH.sub.3                                                                        2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR6##   m.p.  63° C                10   3-Cl, 4-CH.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR7##   m.p.  28° C                11   2,5-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR8##   n.sub.D.sup.20 1.5860             12   2,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR9##   n.sub.D.sup.20 1.5661             13   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR10##  m.p. 102° C                14   4-Cl, 2-CH.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR11##  n.sub.D.sup.20 1.5825             15   4-Cl, 2-CF.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR12##  m.p.  74° C                16   3,5-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR13##  m.p.  63° C                17   2,4,6-Cl.sub.3                                                                           3 CH.sub.3                                                                             CH.sub.3                                                                              ##STR14##  m.p. 111° C                18   1,2,3,4,5-Cl.sub.5                                                                       5 CH.sub.3                                                                             CH.sub.3                                                                              ##STR15##  m.p. 156° C                19     --       0 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                       ##STR16##  n.sub.D.sup.20 1.5689             20   3-CF.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR17##  Hydrochloride  n.sub.D.sup.20                                                 1.5086                            21   4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR18##  m.p. 110° C                22   3-CF.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR19##  n.sub.D.sup.20 1.5351             23   3,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR20##  m.p.  98° C                24   2,5-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR21##  m.p. 110° C                25   2,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR22##  m.p.  67° C                26   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR23##  m.p. 106° C                27   4-CH.sub.3, 3-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR24##  m.p.  94° C                28   4-OCH.sub.3, 3-Cl                                                                        2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR25##  m.p. 120° C                29   2-CH.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR26##  m.p. 118° C                30   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR27##  m.p. 100° C                31   2,4,6-Cl.sub.3                                                                           3 CH.sub.3                                                                             CH.sub.3                                                                              ##STR28##  m.p. 128° C                32   1,2,3,4,5-Cl.sub.5                                                                       5 CH.sub.3                                                                             CH.sub.3                                                                              ##STR29##  m.p. 176° C                33   3,5-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR30##  m.p.  80° C                34     --       0 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                       ##STR31##  n.sub.D.sup.20 1.5723             35     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR32##  m.p.  94° C                36   4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR33##  m.p. 117° C                37   3-CF.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR34##  m.p. 120° C                38   3,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR35##  m.p.  92° C                39   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR36##  m.p. 132° C                40   3,5-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR37##  m.p. 100° C                41   2,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR38##  m.p.  98° C                42   4-Cl, 2-CH.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR39##  m.p.  31° C                43   4-Cl, 2-CF.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR40##  m.p.  90° C                44   3-Cl, 4-OCH.sub.3                                                                        2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR41##  m.p.  89° C                45   3-Cl, 4-CH.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR42##  m.p. 120° C                46     --       0 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                       ##STR43##  m.p.  71° C                47     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR44##  m.p.  93° C                48   3-Cl, 4-CH.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR45##  n.sub.D.sup.20 1.5882             49   3-Cl, 4-OCH.sub.3                                                                        2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR46##  n.sub.D.sup.20 1.5901             50   3,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR47##  n.sub.D.sup.20 1.6042             51   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR48##  m.p. 109° C                52   4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR49##  m.p. 100° C                53   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR50##  m.p.  63° C                54   2,4,6-Cl.sub.3                                                                           3 CH.sub.3                                                                             CH.sub.3                                                                              ##STR51##  m.p. 103° C                55   3,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR52##  n.sub.D.sup.20 1.5959             56   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR53##  m.p.  64° C                57   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR54##  m.p.  86° C                58     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR55##  n.sub.D.sup.20 1.5736             59   4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR56##  n.sub.D.sup.20 1.5842             60     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR57##  n.sub.D.sup.20 1.5380             61   4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR58##  n.sub.D.sup.20 1.5961             62   3,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR59##  n.sub.D.sup.20 1.5866             63   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR60##  m.p.  45° C                64   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR61##  n.sub.D.sup. 20 1.5749            65     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR62##  m.p.  25° C                66   4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR63##  m.p. 104° C                67   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR64##  m.p. 140° C                68   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR65##  m.p. 113° C                69   3-Cl, 4-CH.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR66##  m.p.  70° C                70     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR67##  n.sub.D.sup.20 1.5814             71   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR68##  m.p.  25° C                72   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR69##  n.sub.D.sup.20 1.7087             73   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR70##  m.p. 110° C                74   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR71##  m.p. 120° C                75     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR72##  n.sub.D.sup.20 1.5892             76   4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR73##  n.sub.D.sup.20 1.5864             77   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR74##  m.p. 25° C                 78   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR75##  n.sub.D.sup.20 1.5449             79   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR76##  m.p. 146° C                80   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR77##  m.p. 112° C                81   2,6-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR78##  m.p. 140° C                82   2-CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR79##  m.p. 132° C                83   3=CF.sub.3, 4-Cl                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR80##  m.p.  89° C                84   2-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR81##  m.p. 106° C                85   3-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR82##  m.p.  88° C                86     --       0 H      C.sub.2 H.sub.5                                                                       ##STR83##  m.p. 114° C                87     --       0                                                                                ##STR84##                                                                                   ##STR85##  m.p. 114° C                88     --       0                                                                                ##STR86##                                                                                   ##STR87##  m.p. 140° C                89   3-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR88##  m.p.  58° C                90     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR89##  m.p. 114° C                91   4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR90##  m.p. 126° C                92   3,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR91##  m.p.  93° C                93      --      0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR92##  m.p.  34° C                94     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR93##  n.sub.D.sup.20 1.5836             95     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR94##  n.sub.D.sup.20 1.5750             96     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR95##  m.p. 132° C                97     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR96##  m.p. 166° C                98     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR97##  m.p.  92° C                99     --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR98##  m.p. 124° C                100    --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR99##  m.p. 117° C                101    --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR100## m.p. 130° C                102  3-Cl, 4-CF.sub.3                                                                         2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR101## n.sub.D.sup.20 1.5510             103    --       0 CH.sub.3                                                                              ##STR102##                                                                           ##STR103## m.p.  94° C                104  3,4-Cl.sub.2                                                                             2 CH.sub.3                                                                             OCH.sub.3                                                                             ##STR104## b.p. 150° C/0.05 mm                                                    Hg                                105  4-Cl       1 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR105## n.sub.D.sup.21 1.5760             106  3-Cl,4-OCH.sub.3                                                                         2 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR106## b.p. 180° C/0.02 mmHg                                                  n.sub.D.sup.20 1.5721             107  3-Cl,4-SCH.sub.3                                                                         2 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR107## b.p. 160-180° C/0.1                                                    mmHg n.sub.D.sup.20 1.5700        108    --       0 CH.sub.2CH.sub.2                                                                             ##STR108## m.p. <25° C                109  4-OC.sub.2 H.sub.5                                                                       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR109## m.p. 122° C                110                                                                                 ##STR110##                                                                              1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR111## m.p.  94° C                111  4-SCClF.sub.                                                                             1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR112## m.p.  74° C                112  4-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR113## m.p.  80° C                113  3-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR114## n.sub.D.sup.20 1.5716             114  2-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR115## m.p.  72° C                115  4-Br       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR116## m.p.  82° C                116  4-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR117## m.p.  85° C                117  3-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR118## b.p. 110° C/0.01 mm                                                    Hg                                118  2-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR119## b.p. 115° C/0.1 mm Hg      119  4-Cl       1 H      CH.sub.3                                                                              ##STR120## b.p. 130° C/0.01 mm                                                    Hg                                120  3,4-Cl.sub.2                                                                             2 H      CH.sub.3                                                                              ##STR121## m.p.  78° C                121  3-Cl, 4-CF.sub.3 O                                                                       2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR122## b.p. 160° C/0.01 mm                                                    Hg                                122  4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR123## m.p. 116° C                123  4-CF.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR124## m.p. <25° C                124  3-Cl, 4-ClF.sub.2 CS                                                                     2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR125## m.p.  74° C                125  4-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR126## m.p.  70° C                126  3-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR127## m.p.  89° C                127  4-Br       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR128## m.p. 118° C                128  3-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR129## m.p.  65° C                129  4-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR130## m.p.  74° C                130  3-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR131## b.p. 135° C/0.01 mm                                                    Hg                                131  2-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR132## m.p.  68° C                132  3-CF.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR133## m.p. 120° C                133  4-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR134## m.p.  77° C                134  4-Br       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR135## m.p. 108° C                135  2-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR136## m.p. 100° C                136  2-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR137## m.p. 102° C                137  3-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR138## m.p.  52° C                138  4-Br       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR139## m.p. 172° C                139  2-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR140## m.p. 150° C                140  4-F        1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR141## m.p. 130° C                141    --       0 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR142## b.p. 102-110° C/0.2 mm                                                 Hg n.sub.D.sup.20 1.5498          142    --       0 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR143## b.p.  98-100° C/0.2 mm                                                 Hg n.sub.D.sup.20 1.5700          143  3-Cl 4-CH.sub.3 O                                                                        2 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR144## m.p.  72° C                144  3-Cl 4-CH.sub.3 O                                                                        2 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR145## b.p. 175-180° C/0.2 mm                                                 Hg n.sub.D.sup.20 1.5775          145  3,4-Cl.sub.2                                                                             2 H      C.sub.2 H.sub.5                                                                       ##STR146## m.p.  80° C                146  3-Cl 4-CH.sub.3 S                                                                        2 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR147## b.p. 182° C/0.1 mm Hg                                                  n.sub.D.sup.20 1.5849             147   3-Cl 4-CH.sub.3 S                                                                       2 CH.sub.3                                                                             C.sub.4 H.sub.9                                                                       ##STR148## b.p. 185° C/0.1 mm Hg                                                  n.sub.D.sup.20 1.5742             148    --       0                                                                                ##STR149##                                                                                  ##STR150## Hydrochloride, m.p.                                                           180° C                     149  4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR151## Hydrochloride, m.p.                                                           100° C                     150  4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR152## Hydrochloride, m.p.                                                           110° C                     151  2-CF.sub.3 4-Cl                                                                          2 CH.sub.3                                                                             CH.sub.3                                                                              ##STR153## Hydrochloride, m.p.                                                           140° C                     152    --       0                                                                                ##STR154##                                                                                  ##STR155## Hydrochloride, m.p.                                                           45° C                      153    --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR156## Hydrochloride, m.p.                                                           130° C                     154  3-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR157## Hydrochloride, m.p.                                                           <20° C                     155  4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR158## Hydrochloride, m.p.                                                           170° C                     156  3-CF.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR159## Hydrochloride, m.p.                                                           80° C                      157    --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR160## Hydrochloride, m.p.                                                           150° C                     158  4-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR161## Hydrochloride, m.p.                                                           165° C                     159    --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR162## Hydrochloride, m.p.                                                           110° C                     160    --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR163## Hydrochloride, m.p.                                                           140° C                     161  3-CH.sub.3 1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR164## Hydrochloride, m.p.                                                           <20° C                     162    --       0 CH.sub.3                                                                             CH.sub.3                                                                              ##STR165## Hydrochloride, m.p.                                                           100° C                     163    --       0 CH.sub.3                                                                              ##STR166##                                                                           ##STR167## Hydrochloride, m.p.                                                           120° C                     164  2-Cl       1 CH.sub.3                                                                             CH.sub.3                                                                              ##STR168## Hydrochloride, m.p.                                                           60° C                      __________________________________________________________________________

The active compounds according to the invention possess excellentherbicidal properties and can therefore be used for combating weeds.

Weeds in the broadest sense are plants which grow in places where theyare not desired. As weeds there may be mentioned: dicotyledons, such asmustard (Sinapis), cress (Lepidum), cleavers (Galium), chickweed(Stellaria), camomile (Matricaria), gallant soldier (Galinsoga),goosefoot (Chenopodium), annual nettle (Urtica) and groundsel (Senecio)and monocotyledons, such as timothy (Phleum), bluegrass (Poa), fescue(Festuca), goosegrass (Eleusine), foxtail (Setaria), rye grass (Lolium)and barnyard grass (Echinochloa).

The active compounds according to the invention greatly influence plantgrowth, but in different ways, so that they can be used as selectiveherbicides. They show particular advantages as selective herbicides incultures of cotton, corn and cereals. In higher concentrations, they canalso be employed as total weedkillers (approximately 10-20 kg/ha).

The active compounds according to the present invention can be convertedinto the usual formulations, such as solutions, emulsions, suspensions,powders, pastes and granulates. These may be produced in known manner,for example by mixing the active compounds with extenders, that is,liquid or solid or liquefied gaseous diluents or carriers, optionallywith the use of surface-active agents, that is, emulsifying agentsand/or dispersing agents and/or foam-forming agents. In the case of theuse of water as an extender, organic solvents can, for example, also beused as auxiliary solvents.

As liquid diluents or carriers, they are preferably used aromatichydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes,chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, or strongly polar solvents, such as dimethyl formamide,dimethyl sulfoxide or acetonitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperatures and pressures, for example aerosolpropellants, such as halogenated hydrocarbons, for example freon.

As solid diluents or carriers, there are preferably used ground naturalminerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,montmorillonite or diatomaceous earth, or ground synthetic minerals,such as highly-dispersed silicic acid, alumina or silicates.

Preferred examples of emulsifying and foam-forming agents includenon-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acidesters, polyoxyethylene-fatty alcohol ethers, for examplealkylarylpolyglycol ethers, alkyl sulfonates, alkyl sulfates and arylsulfonates as well as albumin hydrolyzation products; and preferredexamples of dispersing agents include lignin sulfite waste liquors andmethyl cellulose.

The active compounds according to the invention can be present in theformulations as a mixture with other active compounds.

The formulations, in general, contain from 0.1 to 95 percent by weightof active compound, preferably from 0.5 to 90 percent by weight.

The active compounds can be used as such, in the form of theirformulations or in the application forms prepared therefrom, such asready-to-use solutions, emulsions, suspensions, powders, pastes andgranules. They may be used in the customary manner, for example, bywatering, spraying, atomizing, scattering or dusting.

They can be used either by the post-emergence process or by thepre-emergence process; they are preferably used after the emergence ofthe plants.

The amount of active compounds employed can vary within fairly wideranges. It depends essentially on the nature of the desired effect. Ingeneral, the amounts used are from 0.1 to 25 kg/ha, preferably from 0.5to 10 kg/ha.

The present invention also provides a herbicidal composition containingas active ingredient a compound of the present invention in admixturewith a solid or liquefied gaseous diluent or carrier or in admixturewith a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of combating weeds whichcomprises applying to the weeds or a weed habitat a compound of thepresent invention alone or in the form of a composition containing asactive ingredient a compound of the present invention in admixture witha diluent or carrier.

The present invention further provides methods of securing cropsprotected from damage by weeds by being grown in areas in whichimmediately prior to and/or during the time of the growing a compound ofthe present invention was applied alone or in admixture with a diluentor carrier. It will be seen that the usual methods of providing aharvested crop may be improved by the present invention.

The active compounds according to the invention also display a goodacaricidal activity. In addition, the fungicidal action of somecompounds of formula (I), especially against species of cereal mildew,Erysiphe and Puccinia, should be mentioned.

The herbicidal activity of the present compounds is illustrated in thefollowing test Examples.

EXAMPLE A

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amount of solvent, thestated amount of emulsifier was added and the concentrate was thendiluted with water to the desired concentration.

Test plants, which had a weight of 5-15 cm, were sprayed with thepreparation of the active compound so that the amounts of activecompound per unit area stated in the table were applied. Depending onthe concentration of the spray liquor, the amount of water used wasbetween 1,000 and 2,000 1/hectare. After three weeks, the degree ofdamage to the plants was determined and characterized by the values 0-5,which had the following meaning:

0 no effect

1 a few slightly burnt spots

2 marked damage to leaves

3 some leaves and parts of stalks partially dead

4 plant partially destroyed

5 plant completely dead

The active compounds, the amounts applied and the results obtained canbe seen from the following table:

                                      Table A                                     __________________________________________________________________________    Post-emergence test                                                           __________________________________________________________________________                   Amount of                                                                     active com-                                                    Active         pound used,                                                                            Echino-                                                                            Cheno-                                                                            Sina-                                                                             Galin-                                                                            Stella-                                                                           Urti-                                                                             Matri- Cot-                  compound       kg/ha    chloa                                                                              podium                                                                            pis soga                                                                              ria ca  caria                                                                             Oats                                                                             ton                                                                              Wheat              __________________________________________________________________________     ##STR169##    2 1      5 4  5 5 5 4 5 4 5 3 5 3 5 4 4 3                                                                              3 2                                                                              2 0                 ##STR170##    2 1      5 5  5 4 5 5 5 5 5 5 5 5 5 5 4 4                                                                              1                                                                                4 3                 ##STR171##    2 1      5 4  5 4-5                                                                             5 5 5 5 5 4 5 5 5 4 4-5 4                                                                            2 1                                                                              2 1                 ##STR172##    2 1      3 2  2 0 2 0 0 0 0 0 0 0 0 0 2 0                                                                              0 0                                                                              2 1                 ##STR173##    2 1      5 4  4 3 5 5 5 4 5 4 5 5 5 5 4 3                                                                              1 0                                                                              4 3                __________________________________________________________________________

EXAMPLE B

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amount of solvent, thestated amount of emulsifier was added and the concentrate was thendiluted with water to the desired concentration.

Seeds of the test plants were sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It was expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation was of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the test plants was determined andcharacterized by the values 0-5, which had the following meaning:

0 no effect

1 slight damage or delay in growth

2 marked damage or inhibition of growth

3 heavy damage and only deficient development or only 50% emerged

4 plants partially destroyed after germination or only 25% emerged

5 plants completely dead or not emerged.

The active compounds, the amounts applied and the results obtained canbe seen from the following table:

                                      Table B                                     __________________________________________________________________________    Pre-emergence test.                                                           __________________________________________________________________________                    Amount of                                                                     active                                                                        compound                                                      Active          used, Echino-                                                                            Cheno-                                                                            Sina-                                                                             Loli-                                                                             Stella-                                                                            Gali-                                                                             Matri-                                                                            Cot-                      compound        kg/ha chloa                                                                              podium                                                                            pis um  ria  soga                                                                              caria                                                                             ton                                                                              Wheat                                                                             Corn               __________________________________________________________________________     ##STR174##     5 2.5 5 5  5 5 5 5 5 5 5 5  5 5 5 5 1 0                                                                              5 4 3 3                 ##STR175##     5 2.5 5 5  5 5 5 5 5 5 5 5  5 5 5 5 3  2                                                                             4 3 4 3                 ##STR176##     5 2.5 5 5  5 5 5 5 5 5 5 5  5 5 5 5 1 0                                                                              4 4 2 0                 ##STR177##     5 2.5 2 1  2 2 4 3-4                                                                             0 0 2 2  4 3 4-5 3                                                                             2 0                                                                              3 3 1 0                 ##STR178##     5 2.5 5 5  5 5 5 5 5 5 5 5  5 5 5 5 0 0                                                                              2 1 1 0                 ##STR179##     5 2.5 5 5  5 5 5 5 5 4 5 5  5 5 5 5 0 0                                                                              4 3 2 1                 ##STR180##     5 2.5 5 5  5 5 5 5 5 5 5 5  5 5 5 5 2 1                                                                              4 3 4 4                __________________________________________________________________________

It will be understood that the specification and examples areillustrative but not limitative of the present inventon and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. Azolylamidine compound of the formula##SPC19##wherein n is an integer from 0 to 2, inclusive, R¹ isindividually selected from halogen, alkyl, alkoxy, alkylthio,haloalkoxy, haloalkylthio, halophenoxy and haloalkyl and contains notmore than 6 carbon atoms; R² is selected from hydrogen, alkyl, orcycloalkyl and contains not more than 7 carbon atoms; R³ is selectedfrom hydrogen, alkyl, and cycloalkyl and contains not more than 7 carbonatoms; R² and R³, taken together represent a lower alkylene bridge of upto 5 carbon atoms; Az is an imidazolyl radical selected fromimidazol-1-yl and imidazol-1-yl substituted with at least one of alkylof up to 6 carbon atoms, halogen and nitro provided that there is notmore than one nitro substituentand salts thereof with physiologicallytolerated acids.
 2. Azolylamidine compound as claimed in claim 1 whereinn is
 0. 3. Azolylamidine compound as claimed in claim 1 wherein n is 1.4. Azolylamidine compound as claimed in claim 1 wherein n is
 2. 5.Azolylamidine compound as claimed in claim 1 wherein R¹ is halogen. 6.Azolylamidine compound as claimed in claim 1 wherein R¹ is chloro. 7.Azolylamidine compound as claimed in claim 1 wherein R¹ is alkyl. 8.Azolylamide compound as claimed in claim 1 wherein R¹ is alkoxy,alkylthio, haloalkoxy or haloalkylthio.
 9. Azolylamidine compound asclaimed in claim 1 wherein R¹ is halophenoxy.
 10. Azolylamidine compoundas claimed in claim 1 wherein R¹ is haloalkyl.
 11. Azolylamidinecompound as claimed in claim 1 wherein one of R² and R³ is hydrogen. 12.Azolylamidine compound as claimed in claim 1 wherein one of R² and R³ isalkyl.
 13. Azolylamidine compound as claimed in claim 1 wherein R³cycloalkyl.
 14. Azolylamidine compound of the formula ##SPC20##wherein nis an integer of from 0 to 5, inclusive, R¹ is halogen; R² is selectedfrom hydrogen, alkyl, or cycloalkyl and contains not more than 7 carbonatoms; R³ is selected from hydrogen, alkyl, and cycloalkyl and containsnot more than 7 carbon atoms; R² and R³, taken together represent alower alkylene bridge of up to 5 carbon atoms; Az is an imidazolylradical selected from imidazol-1-yl and imidazol-1-yl substituted withat least one of alkyl of up to 6 carbon atoms, halogen and nitroprovided that there is not more than one nitro substituentand saltsthereof with physiologically tolerated acids.
 15. Azolylamidine compoundas claimed in claim 1 wherein R² and R³ taken together are ethylene,tetramethylene or pentamethylene.
 16. Azolyamidine compound as claimedin claim 14 wherein n is
 3. 17. Azolylamidine compound as claimed inclaim 1 wherein Az is imidazolyl substituted with a nitro group. 18.Azolylamidine compound as claimed in claim 1 wherein Az is imidazolylsubstituted with one nitro group and one alkyl group.
 19. Azolylamidinecompound as claimed in claim 1 wherein Az is imidazolyl-1-yl. 20.Azolylamidine compound as claimed in claim 1 wherein Az is imidazolylsubstituted with 2 to 3 chlorine atoms.
 21. Azolylamidine compound asclaimed in claim 1 wherein Az is imidazolyl substituted with two alkylgroups.
 22. Azolylamidine compound as claimed in claim 1 designatedN(4-chlorophenyl)-N',N'-dimethyl-imidazolyl-(1)-amidine. 23.Azolylamidine compound as claimed in claim 1 designatedN-(3-chlorophenyl)-N',N'-dimethyl-imidazolyl-(1)-amidine. 24.Azolylamidine compound as claimed in claim 1 designatedN-(4-fluorophenyl)-N',N'-dimethyl-imidazolyl-(1)-amidine.
 25. Herbicidalcomposition comprising herbicidally acceptable carrier and, in effectiveamounts, an azolylamidine compound as claimed in claim
 1. 26. Method ofcombatting undesired vegetation, which method comprises applying to saidvegetation or its habitat a herbicidally effective amount of anazolylamidine compound of the formula ##SPC21##wherein n is an integerfrom 0 to 2, inclusive, R¹ is individually selected from halogen, alkyl,alkoxy, alkylthio, haloalkoxy, haloalkylthio, halophenoxy and haloalkyland contains not more than 6 carbon atoms; R² is selected from hydrogen,alkyl, or cycloalkyl and contains not more than 7 carbon atoms; R³ isselected from hydrogen, alkyl, and cycloalkyl and contains not more than7 carbon atoms; R² and R³, taken together, represent a lower alkylenebridge of up to 5 carbon atoms; Az is an azolyl radical selected fromimidazol-1-yl and imidazol-1-yl substituted with at least one of alkylof up to 6 carbon atoms, halogen and nitro provided that there is notmore than one nitro substituent.
 27. Method as claimed in claim 26wherein said compound is applied to weeds growing in a crop cultivationto selectively damage the weeds without substantial injury to the crops.28. Method as claimed in claim 26 wherein said compound is selectedfromN-(4-chlorophenyl)-N',N'-dimethyl-imidazolyl-(1)-amidine,N-(3-chlorophenyl)-N',N'-dimethyl-imidazolyl-(1)-amidine,N-(4-fluorophenyl)-N',N'-dimethyl-imidazolyl-(1)-amidine.